Production of elastomeric films

ABSTRACT

A method for producing multi-layered elastomeric film or article, the method comprising: (i) dipping a mould into a composition for producing an elastomeric film having a total solids content of between 5%-40% to produce a layer of elastomeric film composition on the mould, (ii) partially drying the layer of elastomeric film composition on the mould to reduce the total water content of the elastomeric film composition to a level of not less than 22%, (iii) dipping the mould coated with the partially dried layer of elastomeric film composition into a composition for producing an elastomeric film having a total solids content of between 5%-40% to produce a further layer of elastomeric film composition on the mould, (iv) optionally repeating the partial drying step (ii) and the further dipping step (iii), and (v) drying and curing the layers of elastomeric film composition on the mould.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 15/163,839 filed on May 25, 2016, which is a continuationapplication of U.S. application Ser. No. 14/739,012 filed on Jun. 15,2015, which is a divisional application of U.S. application Ser. No.13/147,732 filed on Oct. 18, 2011, which is a U.S. national phaseapplication under 35 USC 371 of international application numberPCT/AU2009/000140, filed Feb. 5, 2009. Each application is incorporatedherein by reference in its entirety for all purposes.

FIELD

The present invention relates to methods for producing elastomericfilms. The method may be used to produce elastomeric film articles suchas gloves.

BACKGROUND

Elastomeric articles such as gloves may be manufactured from naturalrubber or synthetic equivalents. The common process of manufactureinvolves dipping a shaped mould into a tank containing the naturalrubber latex or synthetic polymer to form an elastomeric film on themould.

A single dipping process can produce elastomeric films with a highprobability of having or developing defects, such as a weak spots or pinholes. This can cause problems for products such as gloves as the weakspots or pin holes may expose the wearer to infection or chemicalpermeation depending on the application. Theoretically multiple dippingcan be performed to avoid or limit the risk of defects such as these,but the elastomeric films produced are generally thicker, which isundesirable for products such as gloves due to the reduced sensitivityto the wearer. Another problem associated with multiple dipping methodsis that there can be poor adhesion between the individual layers ofelastomeric film, which increases the risk of pin-hole/barrier defectsand may reduce the durability of the elastomeric film due todelamination between the individual layers. A further problem can bepoor pick-up of the latex composition onto the pre-dipped layer on themould.

There is a need to develop an improved method for producing multilayerelastomeric film products, such as gloves, which results in theproduction of products with improved qualities.

It is desirable for the process to be capable of application to a widerange of polymeric compositions for forming elastomeric films. In someinstances, it is desirable for the product to be free of chemicalirritants, including accelerators in particular. When accelerators arenot used, the process needs to be capable of forming elastomeric filmsand articles which still have the required properties of the desiredthickness, good coating of film layers onto underlying layers,minimisation of pin-hole defects, mechanical strength, durability and/orfreedom from delamination between individual layers.

SUMMARY

According to the present application there is provided a method forproducing multi-layered elastomeric film or article, the methodcomprising:

-   -   (i) dipping a mould into a composition for producing an        elastomeric film having a total solids content of between 5%-40%        to produce a layer of elastomeric film composition on the mould,    -   (ii) partially drying the layer of elastomeric film composition        on the mould to reduce the total water content of the        elastomeric film composition to a level of not less than 22%,    -   (iii) dipping the mould coated with the partially dried layer of        elastomeric film composition into a composition for producing an        elastomeric film having a total solids content of between 5%-40%        to produce a further layer of elastomeric film composition on        the mould,    -   (iv) optionally repeating the partial drying step (ii) and the        further dipping step (iii), and    -   (v) drying and curing the layers of elastomeric film composition        on the mould.

The elastomeric film or article may be in the form of a glove, condom,balloon or another product. When the elastomeric article is a glove, themould is suitably a glove or hand-shaped mould.

The present application also provides elastomeric films and articles,such as gloves, condoms or balloons, produced by the method.

The method may further comprise the steps of:

-   -   (a) dipping the mould into a coagulant containing multivalent        ions in solution,    -   (b) drying or partially drying the coagulant-dipped mould,        prior to step (i).

Typically, during the partial drying step (ii), the maximum film surfacetemperature of the elastomeric film composition on the mould is between25° C.-85° C.

It has been found by the applicant that it is very important to onlypartially dry each layer of elastomeric film composition on the mouldprior to applying a subsequent layer of elastomeric film composition. Inparticular, the applicant has found that it is important that the watercontent in the partially dried elastomeric film composition on the mouldis no less than 22% when the mould is dipped again to form a furtherlayer. The water content of not less than 22% reflects that some liquidremains in the layer of elastomeric film composition. This water contentenables subsequent layers of elastomeric film composition to be appliedand to adhere, spread evenly across and penetrate into the underlyinglayer, to assist in the avoidance of pin-point or barrier defects andde-laminating in the film. This also assists in the durability of thefilm. Previously, it was considered necessary to completely dry eachlayer of elastomeric film composition when preparing a multilayeredelastomeric film. However, this is not the case, and surprisinglyimproved properties flow from partially drying the elastomeric filmcomposition under the conditions referred to in step (ii) prior to theapplication of subsequent layers of elastomeric film composition.

The dipping is performed at least twice, with the intermediate partialdrying step as described above. As indicated in step (iv), steps (ii)and (iii) can optionally be repeated one or more times, to produce filmsand articles comprising 3 or more layers. The final elastomeric film orarticle can, for example, comprise 2 to 15 layers, preferably 2 to 10layers, more preferably 3 to 6 layers of composition.

DETAILED DESCRIPTION

The method for producing multi-layered elastomeric film or articles issuitable for manufacturing polymer gloves, including “disposablegloves”. Conventionally, polymer gloves are used to avoid contamination,i.e. in food handling or in hospitals where there is a risk of transferof infection on contact with sites of infection. Polymer gloves are alsoused to avoid the transfer of disease via skin contact between patientand examiner, when physical examination is carried out.

Disposable gloves are usually thinner than non-disposable gloves, wherethe reduced cost of manufacture of a thinner glove means it iscost-effective to dispose of the glove after a single or several uses.Longer-lasting gloves tend to be thicker, for greater durability andlifespan. Both disposable and longer-lasting gloves can be producedusing the method of the present application.

The physical properties of disposable gloves, usually include a snugtight fit of a thin elastomeric film to facilitate sensitivity to touchby the wearer. At the same time, sufficient elongation is required toensure the glove can be stretched to facilitate insertion of thewearer's hand into the glove with relative ease and without damage tothe glove. Other important properties are minimizing from barrierdefects such as pin-holes.

The method of the invention may also be used to form other elastomericarticles such as condoms and balloons.

Composition

The composition for producing an elastomeric film suitably comprises adispersion or emulsion of an elastomer-forming polymer in a liquid. Thecomposition generally comprises an elastomer-forming polymer and across-linking agent in a liquid medium. The liquid medium is typicallywater, although other solvents can be used. An emulsifier and otheroptional components, as described in further detail below, may also bepresent in the composition.

The total solids content of the composition for forming the elastomericfilm is between 5%-40% by weight of the composition. The percentage oftotal solids content (TSC%) can vary within this range. The solids arediluted with liquid (such as water) to reach the desired concentration.Generally, for forming a thin or disposable type of glove, the totalsolids content will be towards the lower end of this range—and withinone of the following ranges: 2-30%, 4-30%, 4-20%, 5-20%. For formingthicker gloves, the total solids content will tend to be higher, or theglove will be produced from many more layers. Thus, for thicker gloves,the total solids content will tend to be within one of the followingranges: 4-40%, 5-40%, 5-30%, 5-20%, 10-40%, 10-30%, 15-40%, 15-30%.

Elastomer-Forming Polymers

Elastomer-forming polymers include natural rubber and syntheticelastomer-forming polymers, which can be cross-linked to produceelastomeric films. The polymer may be a single polymer or a combinationof two or more polymers. The polymer may be a homopolymer or aco-polymer.

The synthetic elastomer-forming polymer may be a polymer containing freeionically cross-linkable groups, covalently cross-linkable groups, or acombination of both. Examples of ionically cross-linkable groups areacids, including carboxylates, sulfonates and acid anhydrides, and anexample of a covalently cross-linkable group is a double bond.

Synthetic elastomer-forming polymers include copolymers produced bycopolymerisation of conjugated diene monomers and ethylenicallyunsaturated acid monomers (carboxylated polyacrylonitrile butadienebeing an example of such a copolymer), polyisoprene, polychloropreneand/or polyurethane. Amongst the range of conjugated diene monomers,examples are 1,3-butadiene, iso-prene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and acrylonitrile.Regarding ethylenically unsaturated acid monomers, the acid group may bea carboxyl group, a sulfonic acid group or an acid anhydride group.Examples of ethylenically unsaturated acid monomers include acrylic acidor methacrylic acid; itaconic acid, maleic acid, fumaric acid, maleicanhydride, citraconic anhydride, sytrenesulfonic acid, monobutylfumarate, monobutyl maleate, mono-2-hydroxypropyl maleate, and alkalimetal or ammonium salts thereof.

One notable example of a synthetic elastomer-forming polymer iscarboxylated polyacryonitrile butadiene. This may be provided as amixture of carboxylated nitrile latex and nitrile butadiene rubber.

In the art of the present invention, it is common to refer to the amountof the elastomer-forming polymer as being 100 phr (per hundred parts“rubber”), and for the relative amounts of the remaining components of acomposition for producing an elastomeric film to be calculated as anumber of parts compared to the 100 phr of the elastomer-formingpolymer, by weight. Thus, for an amount of cross-linking agent that is1/100^(th) that of the elastomer-forming polymer in the composition byweight, the amount of cross-linking agent is referred to as 1.0 phr.

It is also common in the art to use the expression “latex” or “rubber”to refer to any elastomer-forming polymer in a general sense.Accordingly, particularly in the examples which follow, it should beunderstood that these terms have been used as short-hand to refer to thepolymer of the dipping composition.

Cross-Linking Agents

Elastomer-forming polymers can be cross-linked with one or morecross-linking agents to produce the elastomeric film. Various types ofcross-linking agents can be used.

Accelerators are one sub-class of cross-linking agents which releasesulphur, or act with sulphur-containing compounds, to acceleratesulphur-based covalent cross-linking of the elastomer-forming polymer.Generally, accelerators can be advantageous as they shorten the curing(vulcanisation) time, lower the curing temperature or decrease theamount of cross-linking agents required to be used in the composition.However, on the negative side, accelerators can give rise to allergicreactions, such as allergic contact dermatitis with symptoms includingerythema, vesicles, papules, pruritus, blisters and/or crusting.Examples of accelerators include the carbamates (eg. zinc dibutyldithiocarbamate); thiurams (eg. tetraethylthiuram disulfide (TMTD) anddiphenylthiourea); thiazoles (eg zinc 2-mercaptobenzothiazole (ZMBT));guanidines (eg. diphenylguanidine) and aldehyde/amine-based accelerators(eg. hexamethylenetetramine). Other examples are well known in the artand can be obtained from various publicly available sources.

Another class of cross-linking agents are the ionic cross-linkingagents, which include metal oxides and peroxides (organic andinorganic). These work by ionically cross-linkingionically-crosslinkable groups in the elastomer-forming polymer. Forexample, when the elastomer-forming polymer is carboxylatedpolyacrylonitrile butadiene, a metal oxide cross-linker works byionically cross-linking the carboxylic acid groups. Examples of suitablemetal oxide cross-linking agents include the divalent metal oxidecross-linking agents, such as lead oxide, magnesium oxide, barium oxide,zinc oxide and mixtures thereof. An example of a peroxide cross-linkingagent is 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, which can bepurchased under the trade name Trigonox 29-40B-pd. Combinations of thesecross-linking agents can also be used.

A further class of cross-linking agents are the covalent cross-linkingagents, which include sulphur and sulphur-containing vulcanising agents.These work by covalently cross-linking unsaturated double bonds presentin the elastomer-forming polymer. The sulphur can be present in the formof elemental sulphur. The sulphur can also be donated by organicsulphuric compounds, for example TMTD (Tetramethylthiuram Disulfide).Sulphur donors such as this one are likely to contribute to chemicalallergies and it is preferred to keep their use to a minimum in themanufacture of gloves when allergic content is an issue. Thus, if used,the sulphur is preferably present in the form of elemental sulphur.

Generally, the amount of cross-linking determines the elasticity of theelastomeric film. Therefore, the amount and type of cross-linking agentwill contribute to the extent of cross-linking and the elasticity of thefinal elastomeric film.

For ionic cross-linking agents such as metal oxide and peroxidecross-linking agents, when used, the amount is preferably in the range0.2-8.0 phr. The amount of metal oxide cross-linking agent is suitablywithin one of the following ranges: 0.2-5.0 phr, 0.2-4.0 phr, 0.2-1.5phr, 1.0-4.5 phr, 0.5-1.5 phr, 0.8-1.6 phr, 0.8-1.2 phr or 1.5-5.0 phr.

In some embodiments the composition for producing an elastomeric film isfree of sulphur. In other embodiments, the cross-linking agent comprisessulphur. Sulfur requires high energy at curing (thus high curingtemperature and/or time) compared to other cross-linking agents.However, sulphur does provide the glove with greater chemicalresistance, and therefore it may be desired for this reason. The amountof sulphur in the composition may be in the range of 0-5.0 phr, and whenpresent, from 0.01 to 5.0 phr, 0.01-3.5 phr, 0.01-3.0 phr 0.01-2.0 phror 0.01-1.0 phr or 0.01-0.5 phr for accelerator-free compositions. Whenthe composition also includes accelerator, the amount of sulphur issuitably between 0.0-3.5 phr, such as 0.01-3.0 phr, 0.01-2.0 phr,0.01-1.5 phr, 0.01-1.0 phr or 0.01-0.5 phr.

According to one embodiment, the composition for producing theelastomeric film is accelerator-free.

According to another embodiment, the composition comprises anaccelerator. When an accelerator is present, the composition may be freeof other cross-linking agents. The amount of accelerator is suitablybetween 0.1-2.0 phr, such as between 0.1-1.5 phr, 0.1-1.0 phr, 0.2-1.0phr, 0.3-2.0 phr, 0.3-1.5 phr or 0.2-0.6 phr.

Preparation of the Composition

The composition for producing an elastomeric film can be prepared bymixing the elastomer-forming polymer with a cross-linking agent, andoptionally one or more additives, in a liquid (eg. water).

Suitable additives that may be included in the composition can includeone or more additives selected from the group consisting of stabilisers,emulsifiers, antioxidants, vulcanising agents, polymerisationinitiators, pigments, fillers, colourising agents and sensitisers.

The preparation of the composition includes steps known in the art, andthe composition can be prepared in a conventional manner. For example,the elastomer-forming polymer can be diluted with a solution of astabilizer, such as potassium hydroxide, ammonium hydroxide and/orsodium hydroxide. The amount of stabiliser used is dependent on thesynthetic polymer employed, the pH of the composition and other factors.The stabiliser can range from 0.1-5.0 phr, e.g. 0.5 to 2 phr, preferably1.0 to 1.5 phr, which is diluted with water, preferably filtered water.

A diluted stabilizer solution can be mixed with the elastomer-formingpolymer. The pH of the mixture is suitably adjusted to between 8.5 to10.5, such as a pH between 9.0 to 10.0. The cross-linking agent(s) canthen be added to the mixture.

Antioxidants, for example Wingstal L (the product of p-cresol anddicyclopentadiene) may be added. The antioxidant may, for example, beadded in an amount ranging from 0.1-5.0 phr, 0.1-3.0 phr, 0.1-1.0 phr or0.3-0.5 phr. Pigments such as titanium dioxide, selected for itspigmentation, to reduce the transparency of the final elastomeric film,may be added in amounts ranging from 0.01-10.0 phr, such as 1.5-2.0 phrand colourants can also be added in the desired amounts. The mixture isthen diluted to the target total solids concentration within the rangeof 5%-40% (or within any narrower range as described previously) by theaddition of a liquid, such as water.

Sensitisers are chemicals that can be used in compositions for producingelastomeric films to control the amount of the composition that willremain coated on the mould during dipping. Examples of sensitisers knownin the art that can be used in the composition for producing anelastomeric film include polyvinyl methylether, polypropylene glycol,ammonium nitrate and ammonium chloride. When used, the amount ofsensitiser will be chosen based on the desired film thickness to remainon the mould during dipping, and will generally be between 0.01-5.0 phr.For thinner films, the amount will generally be between 0.01 to 2.0 phr,e.g. 0.1 to 1.0 phr. When other techniques are used for controlling thefilm thickness on the mould, such as the use of pre-dipping the mouldinto coagulant before undertaking the multiple dipping into thecomposition for producing the elastomeric film, the composition forproducing an elastomeric film may not comprise a sensitiser.

Production of Elastomeric Film

The manufacture of the elastomeric film may use conventional equipment.

Optional Step (a) Dipping the Mould into a Coagulant ContainingMultivalent Ions in Solution

A suitable mould, which is based on the shape of the article to beproduced (eg. flat for a film or glove-shaped for a glove) can be dippedinto a coagulant containing multivalent ions in solution. The dipping ofthe mould into a coagulant containing multivalent ions leaves on thesurface of the mould a thin coating of the charged ions. The chargedions coating can assist in controlling the amount composition forforming the elastomeric film that will subsequently remain on thesurface of the mould after dipping into the composition, through chargeinteractions.

The multivalent ions may be cationic (as in the case of, for example,calcium ion-containing coagulants) or anionic, and the choice will bebased on the identity of the elastomeric polymer.

Generally multivalent metal ion solutions containing multivalent cationsare suited to a broad range of elastomeric polymers. Examples of suchmultivalent metal salt ions are calcium, magnesium, barium, zinc, andaluminium. The counterions may be halides (such as chloride), nitrate,acetate or sulphate, amongst others. In the case of calciumion-containing coagulants, the calcium ions can be provided as asolution of calcium nitrate or calcium chloride.

The coagulant may also include any other agents, such as wetting agents,anti-tack agents and/or mould release agents, such as silicon emulsions,polymer release agents and metallic stearates, examples of which arezinc and calcium stearates.

The concentration of multivalent ions can broadly be in the range of1.0-50% by weight of the coagulant solution (measured as the compound ofthe multivalent ion in the solution of the multivalent ions), dependingon the desired thickness of the elastomeric film layers and the numberof layers to be applied. In the case of thinner layers, theconcentration is suitably in the range of 1.0-20%, 1.0-15%, 1.0-12%,1.5-20%, 1.5-15%, 1.0-10%, 1.5-10%, 4-10%, 5-10%, 5-35%, 7-40%, 8-50%and 5-45%. The amounts of other components such as wetness and anti-tackagents are dependent on the properties desired through the use of theseagents, and will vary accordingly.

The duration or dwell time for the mould in the coagulant is suitablybetween 1 and 30 seconds. In some embodiments, the dwell time for themould in the coagulant is 1 to 10 seconds. In some embodiments, thedwell time for the mould in the coagulant may be longer than 30 seconds.The temperature of the coagulant into which the mould is dipped may, forexample, be between 30° C.-80° C.

Prior to dipping the mould into the coagulant, the mould may besubjected to heating. The heating may form a part of a preliminary mouldwashing and drying procedure. The mould may in this case be heated to asurface temperature in the range of 25° C. to 85° C., for example atemperature in the range of 30° C. to 70° C.

Optional Step (b) Drying or Partially Drying the Coagulant-Dipped Mould

If the mould is dipped into a coagulant, following this step the mouldis dried or partially dried.

Drying (or partial drying) is a step that may be repeated in severalstages during the production of the multi-layered elastomeric film orarticle. At each drying or partial drying step, the drying may beperformed by any suitable technique or equipment known in the art,including the application of hot air or radiant heat, or a dryingradiation source such as infra red (IR) and far IR radiation. This canbe performed in an oven or any other suitable drying equipment orenvironment. In the case of drying in an oven, or under the influence ofhot air or radiant heat, the mould may be passed through the dryingzone, which applies heat at an elevated temperature, for a period oftime that is sufficient to drive off the excess moisture/liquid to asufficient degree of dryness. In the case of drying the coagulantremaining on the mould, the drying zone (such as oven) may for examplebe held at, or apply, heat at a temperature of between 50° C.-250° C.The mould typically remains in this zone (or progresses through thiszone) for a period of time sufficient to reach the target level ofdrying, and optionally a target surface temperature of the coagulant onthe mould. This may be between 25° C.-85° C., for example between 40°C.-70° C.

The surface temperature of a coating on the mould (in this case, thecoagulant) can be tested by any suitable technique. One example involvesthe use of a device to measure the surface temperature of an object bythe infra red energy emitted by the object. An example of a device ofthis type is the Thermo-Hunter, model: PT-2LD produced by Optex Co. Ltd.Other techniques for measuring the surface temperature of the film areknown in the art.

Step (i) Dipping the Mould into a Composition for Producing anElastomeric Film having a Total Solids Content of between 5%-40% toProduce a Layer of Elastomeric Film Composition on the Mould

The mould is dipped into the composition for producing an elastomericfilm, embodiments of which have been described in detail above.

The mould is in the dipping tank for an amount of time to ensure themould is evenly coated, but not so long as to develop a thicker coatingthan necessary. Depending on the required thickness of the coating, thedwell time of the mould in the dipping tank may be between 1-30 seconds,such as between 2.0 to 7.0 seconds.

The temperature of the composition into which the mould is dipped isgenerally within the range of 10° C. to 60° C., such as 10° C. to 50°C., 15° C. to 50° C., 20° C. to 50° C., 25° C. to 50° C. or 25° C. to45° C.

Preferably, the surface temperature of the mould does not exceed thetemperature of the composition for producing an elastomeric film by morethan 80° C. It has been found by the applicant that if the surfacetemperature of the mould is more than 80° C. higher than the temperatureof the composition for producing an elastomeric film, shrinkage of thecoating of elastomeric film composition on the mould may occur. In someembodiments, the surface temperature of the mould is lower than thetemperature of the composition for producing an elastomeric film.However, typically, the surface temperature of the mould is about 20° C.to 60° C. higher than the temperature of the composition for producingan elastomeric film.

Step (ii) Partially Drying the Layer of Elastomeric Film Composition onthe Mould

The coating or layer of elastomeric film composition on the mould isthen partially dried, as opposed to fully dried, to reduce the watercontent but without the water content lowering to such an extent that itfalls below 22%. The partially dried elastomeric film composition has awater content in excess of 22% by weight which reflects that somemoisture remains in the elastomeric film composition layer on the mould.Typically, the elastomeric film composition on the mould is dried to amoisture content between 22% and 80%, for example, to 25% to 75% or 30%to 77% or 25% to 60%.

If the elastomeric film composition on the mould is dried to a watercontent of less than about 22%, the layer of the elastomeric film on themould appears visibly dry and when dipped in a composition for formingan elastomeric film having a total solids content of between 5 to 40%,the composition does not readily adhere to the surface of the driedlayer of elastomeric film composition on the mould. A flow mark alsobecomes visible, and the final product displays shrinkage and/or weakspots. The coating may also be uneven.

The partial drying may be conducted using the same type of dryingtechnique as described above in relation to step (b), using conditionsnecessary to reach a state of partial dryness.

The partial drying may be performed by any suitable technique orequipment known in the art, including the application of hot air orradiant heat, or a drying radiation source such as infra red (IR) andfar IR radiation. This can be performed in an oven or any other suitabledrying equipment or environment.

In the case of partial drying in an oven, or under the influence of hotair or radiant heat, the mould bearing the layer or coating ofelastomeric film composition may be passed through the drying zone,which applies heat at an elevated temperature, for a period of time thatis sufficient to drive off some of the excess moisture/liquid to asufficient degree of partial dryness. In this case, the drying zone(such as oven) may be held at, or apply, heat at a temperature ofbetween 50° C.-300° C. (depending on the drying time). This time periodmay be between 2-300 seconds (depending on the temperature of the oven).Generally, the higher the oven temperature, the shorter the time periodin the drying zone, and vice versa.

Generally, during the partial drying, the mould remains in the dryingzone (or progresses through this zone) for a period of time sufficientto raise the surface temperature of the layer of elastomeric filmcomposition on the mould to a maximum temperature between 25° C. and 85°C., e.g. 40° C. to 80° C. If a higher surface temperature is reached,excessive or uneven drying may occur. In addition, the elastomeric filmcomposition on the mould may require cooling prior to the next dippingstep. An additional cooling step may result in delays or additionalcosts in the manufacture of the elastomeric film or article.

The surface temperature of the elastomeric film composition on the mouldcan be measured using the same techniques described above with respectto the coagulant layer surface temperature.

The partial drying is required to reduce the water content of theelastomeric film composition on the mould. The water content of thepartially dried elastomeric film composition is greater than 22%. Thewater content of the elastomeric film composition on the mould can bedetermined by measuring the mass of a sample product at the point ofcompletion of the partial drying step, and then driving off theremaining moisture/liquid in the sample product to obtain the dry massof the product, and determining from these two values the total watercontent. Thus, if the single-layered product at this point in timeweighs 100 mg, and the dried product weighs 90 mg, the water content is10%.

Step (iii) Dipping the Mould Coated with the Partially Dried Layer ofElastomeric Film Composition into a Composition for Producing anElastomeric Film having a Total Solids Content of between 5%-40% toProduce a Further Layer of Elastomeric Film Composition on the Mould

The mould coated with the partially dried layer of elastomeric filmcomposition is dipped into a composition for producing an elastomericfilm. The composition into which the mould is dipped can be the same asor different to the composition used to form the first layer. Thecomposition may differ with respect to the identity and/or amount of theelastomer-forming polymer, the identity and/or amount of anycross-linking agent, the identity and/or amount of other additives, andthe total solids content. In some embodiments, the identity of theelastomer-forming polymer in the second composition is the same as thatused in the first composition. In such embodiments, the amount of thecross-linking agent is also typically the same. In other embodiments,the identity of the elastomer-forming polymer of the second compositionis different to that in the first composition. The total solids contentof the second composition may be the same or different to that of thefirst composition. The total solids content will depend in part on thedesired thickness of the second (or further) layer being applied.

The dwell time of the mould in the second composition is, for example,between 1 and 30 seconds, such as 1 and 20 seconds, 1 and 10 seconds,such as 2 to 5 seconds.

The temperature of the composition into which the mould is dipped isgenerally within the range of 10° C. to 60° C., such as 10° C. to 50°C., 15° C. to 50° C., 20° C. to 50° C., 25° C. to 50° C. or 25° C. to45° C.

Preferably, the surface temperature of the partially dried layer ofelastomeric film composition on the mould does not exceed thetemperature of the composition for forming an elastomeric film by morethan about 80° C. It has been found by the applicant that if the surfacetemperature is more than about 80° C. higher than the temperature of thecomposition for forming an elastomeric film, shrinkage of theelastomeric film composition on the mould may occur. In someembodiments, the surface temperature is lower than the temperature ofthe composition for forming an elastomeric film. However, typically, thesurface temperature is about 20° C. to 60° C. higher than thetemperature of the composition for forming an elastomeric film.

Step (iv) Optionally Repeating the Partial Drying Step (ii) and theFurther Dipping Step (iii)

The partial drying step and further dipping steps may be repeated. Thesesteps are suitably repeated at least once, and may be repeated multipletimes. For each repeated step, the conditions may be different comparedto the original partial drying conditions and dipping conditions forproducing the second layer. Thus, as an example, extent of partialdrying, the total solids content of the composition for forming anelastomeric film may differ for each layer.

For each partial drying step, the layer of elastomeric film compositionin the mould is partially dried to reduce the water content of theelastomeric film composition such that water content of the partiallydried layer of elastomeric film on the mould has a water content ofgreater than 22%. This water content is measured by reference to thewater content of the entire elastomeric film layer on the mould (thatis, the elastomeric film layer formed by multiple dipping).

The average thickness of each layer is typically between 6% and 90% ofthe final elastomeric film, with some layers (such as the first layer)suitably being between 30 to 70%, or 40 to 65% of the full filmthickness. The average thickness of each layer is dependent on thenumber of layers of composition forming the final elastomeric film. Thefinal elastomeric film can, for example, consist of 2 to 15 layers, suchas 2 to 10 layers, 2 to 6 layers, or 3 to 6 layers.

Generally, although not always, the greater the number of layers in thefilm, the lower the % TSC of the composition for producing eachsubsequent layer. This is to keep the thickness of the multilayer filmto a minimum. After the first layer, the % TSC of the composition usedto produce each subsequent layer may be in the range 5%-40% TSC, such as5-30% or 5-12% or 10-30% or 10-40% or 10-20%.

Each layer can be of approximately equal thickness, or of differingthickness. For example the 1^(st) layer can be 50%, 2nd layer 30%, 3rdlayer 20% for a 3-layer film. Approximately equal thickness can beachieved by varying the total solids content of the composition of eachlayer and the temperature at which the layer is deposited. Differentmechanisms of deposition can occur for each layer and differentthicknesses can be deposited even if the % TSC is maintained at the samelevel. Accordingly, varying the % TSC is sometimes required to maintainthe same level of thickness. The thickness of the deposited layers canalso vary according to the concentration of multivalent ions in thecoagulant solution, or the amount of any sensitiser present in thecomposition for producing the elastomeric film temperature of thecomposition, and dwelling time of the mould into the composition.

Optional Additional Steps Prior to Drying and Curing

Further steps can be taken to fine-tune the manufacture of theelastomeric film or article. The film or article can be leached toremove extractable components. Suitable conditions for leachingextractable components from the film or article can involve contactingthe film or article with heated water (eg. through immersion) at atemperature between 40 to 60° C. for between 1 to 50 mins. During thisleaching process, a substantial amount of soluble and extractablecomponents (such as surfactant, ionic compounds) can be removed.

In the case of glove manufacture, the glove can be subjected tobeading/cuffing to create a bead or cuff at the wrist end of the glove.

Step (v) Drying and Curing the Layered Elastomeric Film on the Mould

The film or article is then dried and cured. This step can be effectedin an oven with a minimum temperature of 80° C., in the range 80-150°C., or a minimum temperature of 90° C. (such as 90-150° C.) at a minimumtime of 10 minutes, in the range 10-40mins. Other drying and curingtechniques that can be used includes UV curing.

Optional Additional Steps Following Drying and Curing

The film or article can be subjected to one or more further processsteps prior to stripping of the film or article from the mould. Theseoptional steps include cooling, chlorination, post-curing rinsing,polymer coating and additional drying steps.

The film or article is stripped from the mould at the conclusion of theformation process.

Elastomeric Film Features

The thickness of the final film (or article) can, for example, be in therange 0.01-3.0 mm, such as 0.01-0.3 mm, 0.02-0.2 mm, 0.05-0.10 mm,0.03-0.08 mm, or 0.05-0.08 mm (for thin or disposable gloves), and0.2-3.0 mm for thick gloves. The thickness is suitably measured as an“average thickness”, particularly for gloves, using the points ofmeasurement described below.

The film properties can be measured according to ASTM D-412. In oneembodiment in which the thickness (average thickness) of the film ismeasured at 0.03-0.10 mm, the physical features of the film aresuitably: minimum tensile strength of 10.0 Mpa, relatively low inmodulus at 300% of less than 10.0 Mpa and minimum elongation of 500%. Inanother embodiment in which the thickness (average thickness) of thefilm is measured at 0.03-0.10 mm, the physical features of the film aresuitably minimum tensile strength of 14.0 Mpa, relatively low in modulusat 300% of less than 5.0 Mpa and minimum elongation of 500%.

The desired durability of the film is determined by the end use of thearticle. For example, for gloves for non-surgical use, the wearing timeis usually below 3 hrs, and commonly less than 2 hrs. The durability ofthe film can be controlled by the curing conditions. Generally, thehigher the curing temperature, the more durable the elastomeric film.

The term “average thickness” in respect of the thickness of a glove(specifically the multi-layer elastomeric film forming the glove) refersto the average of three thickness measurements, taken at points alongthe layer of the elastomeric film. The measurements are taken at thecuff, the palm and the finger tip. When measuring the thickness ofindividual layers of the glove, the “average thickness” is a referenceto the average thickness of that layer of film, taken at the threemeasurement points. This may be measured in absolute terms (in mm), oras a percentage of the full thickness of the multi-layered glove. Forelastomeric articles, a similar technique using three thicknessmeasurements can be used to determine the “average thickness”.

The method described above can be used to produce a multilayeredelastomeric film or article with reduced potential for defects such aspin holes, weak spots and/or delamination compared to prior artprocesses for producing multilayered elastomeric films in which eachlayer is fully dried prior to applying a subsequent layer. Further, themethod can be used to produce stronger multi-layered elastomeric filmsthan some prior art processes. For thin gloves, of the type used fordisposable applications, the method can be carried out using afilm-forming composition having a very low concentration of solids, andother factors, which assist to keep each coating layer thin.Accordingly, the overall thickness is kept to a minimum. At the sametime, the partial drying step performed between the application of eachlayer of film-forming composition aids to ensure good lamination, oradhesion and coverage, between adjacent layers. Without this step,difficulties are faced in trying to obtain a multi-layer film having thedesired properties.

In the claims and in the preceding description, except where the contextrequires otherwise due to express language or necessary implication, theword “comprise” or variations such as “comprises” or “comprising” isused in an inclusive sense, i.e. to specify the presence of the statedfeatures but not to preclude the presence or addition of furtherfeatures in various embodiments of the invention.

EXAMPLES

The invention will now be described in further detail with reference tothe following non-limiting examples. All tables of compositions and testresults are shown in the Tables section. All testing procedures areshown in the Testing Procedures section.

General Procedures

In the examples set out below, the following general procedure wasutilised to produce elastomeric films, and gloves in particular. Thegeneral procedure was also used to demonstrate the impact (if any) thatcertain processing conditions and components of the elastomeric filmforming compositions have on the quality of multilayer elastomeric filmsproduced.

General Procedure 1.

1.1 Washing

-   -   The mould is subjected to pre-washing, so as to be clean of any        remaining residues following removal of a glove made on the        mould previously. The mould is then dried in an oven at 70° C.,        reaching a surface temperature of around 60° C. (50° C.-63° C.)

1.2 Coagulant Dipping

-   -   The mould is dipped in the coagulant in accordance with the        following parameters:

Operating Parameter Temperature Dwell Time Ca(NO₃)₂ Tank (° C.) (second)(% in water) pH Coagulant See example 2 See example See Dipping Tankdetails - details example generally details 53-62° C.

1.3 Oven Drying

-   -   The mould is dried in accordance with the following parameters:

Operating Parameter Temperature Time Oven (° C.) (second) Coagulant Oven135 38 Blower

1.4 Pre-condition 1

-   -   The oven drying as described in step 1.3 is used to obtain        certain “preconditions” for the coating on the mould, prior to        proceeding to the next step. Pre-condition 1 refers to the        conditions of surface temperature and “dryness” of the mould        coated with coagulant achieved following oven drying, prior to        continuing to the next step. In some examples, pre-condition 1        is manipulated to demonstrate the impact that pre-condition 1        has on the final product. Where the pre-condition is not        specified, it is as set out below:

Operating Parameter Surface temperature Mould Condition of mould(Dryness: Wet/ (° C.) Partially Dry/Dried) Pre-condition 1 See exampleSee example details - of the mould details - Partial Dry/Dried if coatedwith 59° C. if not not specified Ca²⁺ prior to specified dipping

1.5 First stage dipping

-   -   The mould following step 1.4 is dipped into a tank of        composition for forming an elastomeric film, containing the        components specified for the given example. The conditions in        the first stage dipping step are as follows:

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH First See example See example See See stage details. details - 4example example dipping 40-42 if seconds if details details tank not notspecified specified

1.6 Partial drying

-   -   Unless otherwise specified to test the impact of the degree of        drying on the final product, the dipped mould is passed through        an oven held at the temperature for the time indicated below. In        some examples, the degree of drying following the first stage        dipping is modified from this parameter to demonstrate the        impact that a different degree of drying has on the final        product.

Operating Parameter Temperature Time Oven (° C.) (second) Gelling Oven 1120 unless otherwise 12 unless specified. otherwise specified.

1.7 Pre-condition 2

-   -   The partial drying as described in step 1.6 is used to obtain        certain “preconditions” for the layer coated onto the mould,        prior to proceeding to the next step. Pre-condition 2 refers to        the conditions of surface temperature and “dryness” of the mould        coated with the first layer of composition for forming an        elastomeric film achieved following (partial) drying, prior to        continuing to the next step. In some examples, pre-condition 2        is manipulated to demonstrate the impact that pre-condition 2        has on the final product. Where specific conditions for        pre-condition 2 are not specified, the conditions are as set out        below:

Operating Parameter Mould Surface Condition Temperature (Dryness: Wet/of mould Partially Water Content (° C.) Dry/Dried) (%) Pre- Around40-44° C., Partially As specified - condition 2 unless Dried unlessgenerally 85%-22% otherwise otherwise unless specified specifieddifferent conditions tested. Most typically around 50%-70%.1.8 Second stage dipping

-   -   The mould following step 1.7 is dipped into a tank of        composition for forming an elastomeric film, containing the        components specified for the given example. The conditions in        the second stage dipping step are as follows:

Operating Parameter Dwell Temperature Time TSC Tank (° C.) (second) (%)pH Second stage See example See See See dipping tank details. exampleexample example 40-42 if details - details details not specified 4 s. ifnot specified

1.9 Partial drying

-   -   Unless otherwise specified to test the impact of the degree of        drying on the final product, the dipped mould is passed through        an oven held at the indicated temperature for the time indicated        below. In some examples, the degree of drying following the        second stage dipping is modified from this parameter to        demonstrate the impact that a different degree of drying has on        the final product.

Operating Parameter Temperature Time Oven (° C.) (second) Gelling Oven 290-110 unless 12 unless otherwise specified otherwise specified

1.10 Pre-condition 3

-   -   The partial drying as described in step 1.9 is used to obtain        certain “pre-conditions” for the layer coated onto the mould,        prior to proceeding to the next step. Pre-condition 3 refers to        the conditions of surface temperature and “dryness” of the        combination of layers coated on the mould achieved following        (partial) drying, prior to continuing to the next step. In some        examples, pre-condition 3 is manipulated to demonstrate the        impact that pre-condition 3 has on the final product. Where        specific conditions for pre-condition 3 are not specified, the        conditions are as set out below:

Operating Parameter Temperature Mould Condition Surface (Dryness: Wet/Of mould Partially Dry/ Water (° C.) Dried) Content (%) Pre-condition 3About 41, Partially As specified - of the mould unless Dried, unlessgenerally coated with otherwise otherwise 85%-22% 1st and 2^(nd)specified specified unless dipping different compositions conditionstested. Most typically around 50%-70%.

1.11 Third stage dipping

-   -   The mould following step 1.10 is dipped into a tank of        composition for forming an elastomeric film, containing the        components specified for the given example. The conditions in        the third stage dipping step are as follows:

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH Latex See example See example See See Dipping details. details.example example Tank 3 About 30 About 4 if details details (29-34) notif not specified specified

1.12 Beading

-   -   The product following third stage dipping is subjected to        beading.

1.13 Drying

-   -   The product following third stage dipping, and beading, is oven        dried at a temperature between 80° C. and 120° C. for around 60        seconds.

1.14 Pre-cure leaching

-   -   Pre-leaching is conducted by rinsing in warm water for a short        period of time.    -   The beading, drying and pre-cure leaching steps could be carried        out in any order. The processes of beading and pre-cure leaching        could be exchange depending on the quality of cuff beading.

1.15 Curing

-   -   Oven curing is conducted through ovens having 4 zones set at        successive temperatures of 118, 105, 135 and 108° C., taking        approximately 4-6 minutes to progress through each zone.

1.16 Post curing steps

-   -   The product is water cooled, chlorinated in a 745 ppm chorine        solution at pH 2.0 held at 52° C. for 50 seconds, neutralized        and rinsed in water, dried and stripped from the mould. 30

Example 1

Gloves were produced using Procedure 2, which is within the framework ofGeneral Procedure 1, from Glove Composition 1 outlined in Table 1. It isnoted that some parameters varied a little between individual samples,and where this occurred this is indicated by a range that covers thevariations.

The gloves produced were of good quality, with good adhesion between thelayers of elastomeric film, good pick-up of latex composition, no latexflow mark, no rubber lump formation, no thin or weak spots, no pin-holesand no shrinkage. The gloves were found to have an average durabilitytime of 4 hours (4.012 hours) when subjected to the durability test over50 samples.

Procedure 2:

1.1 Washing as described in General Procedure 1.

1.2 Coagulant dipping in accordance with the following parameters.

Operating Parameter Temperature Dwell Time Ca(NO₃)₂ Tank (° C.) (second)(% in water) pH Coagulant 53-57 2 10.1-10.8 7.2-7.5 Dipping Tank

1.3 Oven drying in accordance with the following parameters:

Operating Parameter Temperature Time Oven (° C.) (second) Coagulant Oven135 38 Blower

1.4 Pre-condition 1 parameters:

Operating Parameter Surface temperature Mould Condition of mould(Dryness: Wet/ (° C.) Partially Dry/Dried) Pre-condition 1 59 PartiallyDry/Dried

1.5 First stage dipping parameters:

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH Dipping Target 40 4 Target Target Tank 1 (between 17.0 9.2 40-42)(16.8-17.4) (9.0-9.3)

1.6 Partial drying parameters as described in General Procedure 1 (120°C. for 12 seconds).

1.7 Pre-condition 2 parameters:

Operating Parameter Surface Mould Condition Temperature (Dryness: Wet/of mould Partially Dry/ Water (° C.) Dried) Content (%) Pre- 44Partially Dried 67.28 condition 2

1.8 Second stage dipping parameters:

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH Dipping Target 37 4 15.9 Target Tank 2 (37-40) (15.8-16.5) 9.0(9.2-9.3)

1.9 Partial drying parameters as described in General Procedure 1(90-110° C. for 12 seconds).

1.10 Pre-condition 3 parameters:

Operating Parameter Surface Mould Temperature Condition Pre- Of mould(Dryness: Water condition (° C.) Wet/Partially Content 3 Dry/Dried) (%)41 Partially 57.50 Dried

1.11 Third stage dipping parameters:

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH Dipping Target 4 18.2 (+/−0.2) 9.2 (+/−0.1) Tank 3 30 (29−34)

1.12-1.16 Steps were performed as outlined in General Procedure 1.

Example 2

This example demonstrates multilayer gloves can be made when usingdifferent process conditions and a different composition to that used inExample 1 above. Gloves were produced using Procedure 3, which is withinthe framework of General Procedure 1, from Glove Composition 2 outlinedin Table 2. It is noted that some parameters varied a little betweenindividual samples, and where this occurred is indicated by the rangethat covers the variations.

The gloves produced were of good quality, with good adhesion between thelayers of elastomeric film, good pick-up of latex composition, no latexflow mark, no rubber lump formation, no thin or weak spots, no pin-holesand no shrinkage. The gloves were found to have an average durabilitytime of 3 hours 53 minutes (3.875 hours) when subjected to thedurability test over 50 samples.

Procedure 3:

1.1 Washing as described in General Procedure 1.

1.2 Coagulant dipping in accordance with the following parameters. It isnoted that the calcium concentration is lower and the pH higher than forProcedure 2 in order to form a thinner film.

Operating Parameter Temperature Dwell Time Ca(NO₃)₂ Tank (° C.) (second)(% in water) pH Coagulant 56 2 6.9 8.7 Dipping Tank

1.3 Oven drying in accordance with the following parameters:

Operating Parameter Temperature Time Oven (° C.) (second) Coagulant 13538 Oven Blower

1.4 Pre-condition 1 parameters:

Operating Parameter Surface Pre- temperature Mould Condition conditionof mould (Dryness:Wet/ 1 (° C.) Partially Dry/Dried) 59 PartialDry/Dried

1.5 First stage dipping parameters:

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH Dipping 40 4 14.3 9.6 Tank 1

1.6 Partial drying parameters as described in General Procedure 1 (120°C. for 12 seconds).

1.7 Pre-condition 2 parameters:

Operating Parameter Surface Mould Condition Temperature (Dryness: Wet/Water Pre- of mould Partially Dry/ Content condition 2 (° C.) Dried) (%)40 Partially Dried 73.98

1.8 Second stage dipping parameters. It is noted that the total solidscontent is lower than that used in Procedure 2.

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH Dipping 37 4 14.1 9.8 Tank 2

1.9 Partial drying parameters as described in General Procedure 1(90-110° C. for 12 seconds).

1.10 Pre-condition 3 parameters:

Operating Parameter Mould Condition Temperature (Dryness: Pre- SurfaceWet/ condition Of mould Partially Water 3 (° C.) Dry/Dried) Content (%)41 Partially 65.64 Dried

1.11 Third stage dipping parameters. It is noted that the TSC is lowerthan that used in Example 1.

Operating Parameter Temperature Dwell Time TSC Tank (° C.) (second) (%)pH Dipping 30 4 17.8 9.6 Tank 3

1.12-1.16 Steps were performed as outlined in General Procedure 1.

Example 3

Example 3 demonstrates that multilayer gloves can be made when using arange of different process conditions within the invention and a rangeof different glove compositions. The glove compositions tested inExample 3 are those of Glove Composition 3 outlined in the combinationof Tables 3 and 4. The compositions tested in this Example containvarying amounts of metal oxide crosslinking agent (MgO was the testmetal oxide), or non-metal oxide (TETD was the test agent), combinedwith varying concentrations of coagulant solution and varying totalsolids contents of the latex composition. The various combinations ofvariants produced 48 different glove samples. The compositions in thisexample were accelerator-free.

The process used to produce the gloves was General Procedure 1, in whichthe parameters were controlled as outlined in the Table 6. Thecombinations of cross-linking agent, concentration of coagulantsolution, the total solids content of the composition for forming anelastomeric film and dwell time used are shown in Table 6. The thicknessof the various layers formed was measured for some of the multi-layeredelastomeric gloves produced. The extent of barrier defects, durability,stickiness and evenness of coating for the multi-layered elastomericgloves produced were assessed as described in the Testing Techniquesection at the end of the Examples. The results are shown in Table 6.

Gloves were also produced from the Glove Composition 4 outlined in Table5 which contains 1.50 phr of ZnO and 0.20 phr of sulphur as crosslinkingagent, 0.2 phr of antioxidant, and no accelerator. The procedure was asdescribed for the production of gloves in Example 3. The gloves producedfrom the accelerator-free compositions were of good quality.

Example 4

Example 4 was conducted to confirm and demonstrate the finding thatimproved glove quality can be achieved by only partially drying eachlayer of composition prior to applying the next layer of composition forforming the elastomeric film. The test results also determined anddemonstrate a range of favourable conditions of water contents andsurface temperatures for easy coating.

This example was conducted in two parts. In both parts of Example 4,Glove Composition 1 was utilised as the test composition.

Other tests were conducted (results not reported), on correspondingcompositions containing between 0.2 to 4.0 phr of MgO, BaO, Al₂O₃,peroxide and DPG as the cross-linking agents. The results confirmed thatthe partial drying principle applies equally to compositions containingthese cross-linking agents.

In the first part, the temperature of the drying oven was kept at aconstant 120° C., and the time that the mould coated with the firstlayer of composition was in the oven prior to the dipping in a secondlayer of composition was adjusted from 0 seconds up to 1000 seconds. Forthe samples dried for a time of 240 seconds or less, the glove wassubjected to a second stage of partial drying followed by a thirddipping to produce a third layer of composition. The third stage dippingwas not performed for samples dried for more than 240 seconds, as the2-layer products were already showing signs of poor quality.

This test revealed the impact that greater drying times have on thesurface temperature of the coating on the mould, on the water content ofthe layer, and then on the product quality of the glove produced.

The first part of Example 4 was conducted in accordance with GeneralProcedure 1, with the following parameters:

Step 1.2 Coagulant dipping at 60° C. (58 to 61° C.), pH 7.6, 8.7%Ca(NO₃)₂.

Step 1.3 Oven set at 120° C.

Step 1.4 Surface temperature of about 59° C. (between 53 to 70° C.)

Step 1.5 Dipping in Glove Composition 1 at 16.7% total solidsconcentration, pH 9.7, 29° C. for 5 seconds Step 1.6 Partial drying at120° C. for the time period indicated in the first column of Table 7

Step 1.7 Pre-condition 2 as indicated in Table 7

Step 1.8 Dipping in Glove Composition 1 at 16.7% total solidsconcentration, pH 9.7, 29° C. for 5 seconds

Steps 1.9-1.11 conducted for samples dried in drying oven 1 for up to240 seconds, but not conducted for samples dried for more than 240seconds previously (2 layers only); corresponding water contentscalculated at the end of the procedure.

Step 1.9 Partial drying 2 conducted at 120° C. for the time periodindicated in Table 7 (0 to 240 seconds)

Step 1.10 Pre-condition 3 as indicated in Table 7.

Step 1.11 Dipping in Glove Composition 1 at 16.7% total solidsconcentration, pH 9.7, 29° C. for 5 seconds.

Steps 1.12-1.16 as described in General Procedure 1.

The results of Example 4 part 1 are shown in Table 7.

In the second part, the temperature of the drying oven following firststage dipping was kept at a constant 120° C., but this time thefirst-layer coated mould was held in the oven for a time of between 240seconds and 1000 seconds as indicated in Table 8, followed by cooling toreduce the surface temperature to 40° C. The heating and cooling wasfollowed by the second stage dipping. This test explored whether theimportant factor to control in the process was the surface temperatureof the layer of film prior to dipping a subsequent layer, or the watercontent.

The second part of Example 4 was conducted in accordance with GeneralProcedure 1, with the following parameters:

Step 1.2 Coagulant dipping at 60° C. (58 to 62° C.), pH 7.6, 8.6%Ca(NO₃)₂.

Step 1.3 Oven set at 120° C.

Step 1.4 Surface temperature of about 59° C. (between 56 to 70° C.)

Step 1.5 Dipping in Glove Composition 1 at 17% total solidsconcentration, pH 9.7, 25° C. for 5 seconds

Step 1.6 Partial drying at 120° C. for a time period between 240 secondsand 1000 seconds, as indicated in Table 8

Step 1.7 Allowing the surface to cool to about 40° C., beforeprogressing to step 1.8; corresponding water content calculated at theend of the procedure.

Step 1.8 Dipping in Glove Composition 1 at 17% total solidsconcentration, pH 9.7, 25° C. for 5 seconds

Steps 1.9-1.11 not conducted (2 layers only)

Steps 1.12-1.16 as described in General Procedure 1.

The results of Example 4 part 2 are shown in Table 8.

The combination of the test results for parts 1 and 2 of Example 4 showthat the important factor to control is the water content, and thatpartial drying should not be progressed to an extent such that the watercontent of the layers of composition falls below 22%. Below this watercontent level the glove quality drops off, with a poor pick-up of thecomposition (poor adhesion between the layers) and an increase inshrinkage.

Example 5

Example 5 was conducted to confirm and demonstrate the finding thatimproved glove quality can be achieved by only partially drying eachlayer of composition prior to applying the next layer of composition forforming the elastomeric film.

In Example 5, the impact of different levels of drying before each layeris coated onto the mould was tested. In part A, the impact of differentdrying levels of the coagulant before the first layer was dipped wastested, in part B the impact of different drying levels of the firstlayer before the second layer was dipped was tested, and in part C, theimpact of the different drying levels of the second layer before thethird layer was dipped was tested. In all other respects, the processconditions were kept uniform.

The tests were conducted using Glove Composition 1, and GeneralProcedure 1, with the process parameters controlled as outlined inTables 9A, 9B and 9C, and as follows:

Step 1.2 Coagulant dipping at 60° C. (58 to 61° C.), 9.3% Ca(NO₃)₂, pH7.8.

Step 1.3 For part 9A, the oven temperature was set to a suitable level,and the time in the oven controlled, to get to a surface temperature inthe target range for testing, the target range being set out in the lefthand column of Table 9A. In some cases no drying in the oven wasrequired—instead the layers were allowed to cool in ambient conditions.For parts 9B and 9C, the oven was set to 120° C.

Step 1.4 For part 9A, the surface temperature was as identified in Table9A. For parts 9B and 9C, the surface temperature was around 59° C.(between 59° C. and 81° C.)

Step 1.5 Dipping in Glove Composition 1 at 17.5% total solidsconcentration, pH 9.7, 29° C. for 5 seconds

Step 1.6 For part 9A, the oven was set to 120° C. and observations weremade on the coating quality and recorded under “Observations after1^(st) dip layer”. The testing ended for part 9A here. For part 9B, theoven temperature was set to the necessary level to achieve a surfacetemperature for the first layer on the mould to be within the targetrange for testing. The target range is set out in the left hand columnof Table 9B. For part 9C, the oven was set to 120° C. for partialdrying.

Step 1.7 The surface temperature for Pre-condition 2 for part 9B isindicated in Table 9B. The surface temperature for part 9C was between45° C. and 52° C.

Step 1.8 Dipping in Glove Composition 1 at 17.5% total solidsconcentration, pH 9.7, 29° C. for 5 seconds for parts 9B and 9C.

Step 1.9 The oven temperature for part 9B was set to 120° C. andobservations were made on the coating quality and recorded under“Observations after 2^(nd) dip layer” in Table 9B. The testing ended forpart 9B here. The degree of drying for part 9C was controlled to attemptto reach the desired surface temperature range indicated in the lefthand column of Table 9C. The oven temperature was set to a suitablelevel, and the time in the oven controlled, to get to a surfacetemperature in this range. In some cases no drying in the oven wasrequired—instead the layers were allowed to cool in ambient conditions.

Step 1.10 The surface temperature for Pre-condition 3 for part 9C isindicated in Table 9C.

Step 1.11 Dipping in Glove Composition 1 at 17.5% total solidsconcentration, pH 9.7, 29° C. for 5 seconds for part 9C.

Step 1.12 The product from step 1.11 was dried in an oven at 120° C.,while observations were made and recorded under “Observations on 3^(rd)dip layer” in Table 9C.

In this example, the drying conditions were varied to determine anddemonstrate the properties of films/gloves produced with a differentextent of drying of the layers of elastomeric film on the mould prior toapplication of a further layer of elastomeric film.

Changes were made to the surface temperature of the mould prior to thefirst dipping in the composition for forming an elastomeric film(pre-condition 1) and to the water content and surface temperature ofthe layers of elastomeric film on the mould prior to the second andthird dipping in the composition for forming an elastomeric film(pre-conditions 2 and 3).

Total water content, latex pick up, flow marks, lumping, weak spots, pinholes and shrinkage of the layers after dipping were assessed.

The results of the assessment are set out in Tables 9A to 9C. Table 9Asets out the results of the experiment conducted to examine the effectof changes to pre-condition 1 on the formation of the first layer ofelastomeric film. Table 9B sets out the results of the experimentconducted to examine the effect of changes to pre-condition 2 on theformation of the second layer of elastomeric film. Table 9C sets out theresults of the experiment conducted to examine the effect of changes topre-condition 3 on the formation of the third layer of elastomeric film.It is noted that the procedure used to determine the water content of aparticular product results in destruction of the product, and thereforeseparate trials were required to build up the water content results foreach layer, giving the set of tables A, B and C.

In these tables, “dried” refers to a water content of between 1-22%, and“partially dried” refers to a water content of >22%.

The results show that the water content of the films following drying(specifically, partial drying) is critical to the properties of thefilm/glove produced. The results also show that the surface temperatureis not critical for easy/good coating, provided that the necessary watercontent corresponding to partial drying is achieved.

Example 6

Example 6 was conducted to investigate in more detail the impact thathigher drying temperatures (combined with shorter drying times) have onthe elastomeric films/gloves produced in the process. It was desired toinvestigate the effect of changes in the water content and surfacetemperature of the layer or layers of elastomeric film on the mouldfollowing application of a further layer of elastomeric film (e.g. theeffect of changes to pre-condition 2).

The tests were conducted using Glove Composition 1, and GeneralProcedure 1, with the process parameters controlled as follows:

Step 1.2 Coagulant dipping at 60° C. (60 to 62° C.), pH 7.9, 9.7%Ca(NO₃)₂.

Step 1.3 Oven set at 120° C.

Step 1.4 Surface temperature of about 59° C. (between 55 to 68° C.)

Step 1.5 Dipping in Glove Composition 1 at 17.2% total solidsconcentration, pH 9.7, at a temperature between 25° C.-29° C. for 5seconds

Step 1.6 Drying at a high temperature of 247° C. for a time periodbetween 10 seconds and 350 seconds, as indicated in Table 10

Step 1.7 Pre-condition 2 details including the surface temperature wascalculated for two samples and averaged. At the end of the procedure thewater content was also calculated and recorded. The averaged data ispresented in Table 10.

Step 1.8 Dipping in Glove Composition 1 at 17.2% total solidsconcentration, pH 9.7, 26° C.-29° C. for 5 seconds. Observations werethen made on the quality of the coating on the mould following thissecond dipping.

Steps 1.9-1.11 not conducted (2 layers only)

Steps 1.12-1.16 as described in General Procedure 1.

The results of this Example show that the combination of a high surfacetemperature with low water content (lower than 22%) results in coatingdifficulties and a poor product. The results also show that acombination of a lower surface temperature with a higher water content(one above 22%) result in a good quality of coating. Thirdly, theresults show that when the water content is low due to the fast/highheating conditions, but the surface temperature is within the rangefound to give good coating results in previous examples (due to theshort time of heating), despite the good surface temperature, thecoating quality and product is poor. This shows that the critical factorto control to achieve optimum coating and product quality is the watercontent, and not the surface temperature or duration of heating.

Glove Compositions used in Examples:

TABLE 1 Glove Composition 1 Ingredient Part per hundred of dry “rubber”phr Carboxylated Nitrile Butadiene Rubber 100 Potassium Hydroxide 1.50Cross-linking agent (i) Zinc Oxide 0.70 (ii)Sulfur 1.10 Accelerator (i)Zinc Dibutyl Dithiocarbamate 0.65 Antioxidant (i) Wingstal L (theproduct of 0.20 p-cresol and dicyclopentadiene) Titanium Dioxide 3.50Colorant: Flexobrite Blue BRN 0.14 Water Amount to reach TSC

TABLE 2 Glove Composition 2 Ingredient Part per hundred of dry “rubber”phr Carboxylated Nitrile Butadiene Rubber 100 Potassium Hydroxide 1.50Cross-linking agent (i) Zinc Oxide 1.07 (ii) Sulfur 1.05 Accelerator (i)Zinc Dibutyl Dithiocarbamate 0.35 Antioxidant (i) Wingstal L (theproduct of 0.20 p-cresol and dicyclopentadiene) Titanium Dioxide 4.00Colorant: Flexobrite Violet 411/78S 0.32 Flexobrite Sky Blue 72249 0.19Flexobrite Carmine 11/78 0.01 Water Amount to reach TSC

TABLE 3 Glove Composition 3 Ingredient Part per hundred of dry “rubber”phr Carboxylated Nitrile Butadiene Rubber 100 Potassium Hydroxide 1.5Cross-linking agent (i) Metallic Oxide/ As shown Non Metallic Oxide inTable 4 (ii) Sulfur 0.10 Antioxidant (i) Wingstal L (the product of 0.40p-cresol and dicyclopentadiene) Titanium Dioxide 4.0 Colorant:Flexobrite Violet 411/78S 0.14 Flexobrite Sky Blue 72249 0.09 FlexobriteCarmine 11/78 0.01 Water Amount to reach TSC

TABLE 4 Cross-linking agent (CLA) used and amount Cross-Linking Part perhundred Agent of dry rubber MgO (Magnesium Oxide) 0.5 2.0 4.0 8.0 TETD0.5 2.0 4.0 8.0 (Tetraethylthiuramdisulfide)

TABLE 5 Glove Composition 4 Ingredient Part per hundred of dry “rubber”phr Carboxylated Nitrile Butadiene Rubber 100 Potassium Hydroxide 1.50Cross-linking agent (i) Zinc Oxide 1.50 (ii) Sulfur 0.20 Antioxidant (i)Wingstal L (the product of 0.20 p-cresol and dicyclopentadiene) TitaniumDioxide 4.00 Colorant: Flexobrite Violet 411/78S 0.14 Flexobrite SkyBlue 72249 0.09 Flexobrite Carmine 11/78 0.01 Water Amount to reach TSC

Test Result Tables

TABLE 6 Barrier Defect Coagulant Compliance Solution Latex Thickness(mm) to ASTM Evenness Ca(NO₃)₂ TSC Temp Time Layer Layer Layer WaterD6319 of CLA pHr (%) (%) (° C.) (sec) 1 2 3 Leakage (Pass/Fail)Durability Stickiness Coating MgO 0.5 0.5 3 10 1 0.05 0.05 0.05 1/100Pass OK Minimal Even 5.0 10 25 5 N.C. N.C. N.C. 1/100 Pass Good MinimalEven 10.0 20 40 10 N.C. N.C. N.C. 1/100 Pass Good None Even 15.0 25 5015 N.C. N.C. N.C. 1/100 Pass Good None Even 20.0 30 60 20 0.12 0.04 0.041/100 Pass Good None Even 30.0 40 60 5 0.22 0.04 0.04 0/100 Pass GoodNone Even 2.0 0.5 3 10 1 N.C. N.C. N.C. 1/100 Pass Good Minimal Even 5.010 25 5 N.C. N.C. N.C. 1/100 Pass Good None Even 10.0 20 40 10 N.C. N.C.N.C. 0/100 Pass Good None Even 15.0 25 50 15 N.C. N.C. N.C. 0/100 PassGood None Even 20.0 30 60 20 0.13 0.05 0.04 0/100 Pass Good None Even30.0 40 60 5 0.21 0.04 0.06 0/100 Pass Good None Even 4.0 0.5 3 10 1N.C. N.C. N.C. 1/100 Pass Good None Even 5.0 10 25 5 N.C. N.C. N.C.0/100 Pass Good None Even 10.0 20 40 10 N.C. N.C. N.C. 0/100 Pass GoodNone Even 15.0 25 50 15 N.C. N.C. N.C. 0/100 Pass Good None Even 20.0 3060 20 0.13 0.04 0.04 0/100 Pass Good None Even 30.0 40 60 5 0.21 0.040.05 0/100 Pass Good None Even 8.0 0.5 3 10 1 N.C. N.C. N.C. 1/100 PassGood None Even 5.0 10 25 5 N.C. N.C. N.C. 0/100 Pass Good None Even 10.020 40 10 N.C. N.C. N.C. 0/100 Pass Good None Even 15.0 25 50 15 N.C.N.C. N.C. 0/100 Pass Good None Even 20.0 30 60 20 0.13 0.04 0.04 0/100Pass Good None Even 30.0 40 60 5 0.21 0.04 0.05 0/100 Pass Good NoneEven Barrier Defect Coagulant Compliance Solution Latex Thickness (mm)to ASTM Evenness Ca(NO₃)₂ TSC Temp Time Layer Layer Layer Water D6319Durability of CLA pHr (%) (%) (° C.) (sec) 1 2 3 Leakage (Pass/Fail)(hour) Stickiness Coating TETD 0.5 0.5 3 10 1 N.C. N.C. N.C. 1/100 Pass1 2 1 5.0 10 25 5 N.C. N.C. N.C. 1/100 Pass 1 1 1 10.0 20 40 10 N.C.N.C. N.C. 0/100 Pass 1 1 1 15.0 25 50 15 N.C. N.C. N.C. 0/100 Pass 1 1 120.0 30 60 20 0.13 0.05 0.04 0/100 Pass 1 1 1 30.0 40 60 5 0.21 0.040.06 0/100 Pass 1 1 1 2.0 0.5 3 10 1 N.C. N.C. N.C. 1/100 Pass 1 1 1 5.010 25 5 N.C. N.C. N.C. 1/100 Pass 1 1 1 10.0 20 40 10 N.C. N.C. N.C.0/100 Pass 1 1 1 15.0 25 50 15 N.C. N.C. N.C. 0/100 Pass 1 1 1 20.0 3060 20 0.12 0.05 0.04 0/100 Pass 1 1 1 30.0 40 60 5 0.20 0.05 0.05 0/100Pass 1 1 1 4.0 0.5 3 10 1 N.C. N.C. N.C. 1/100 Pass 1 1 1 5.0 10 25 5N.C. N.C. N.C. 0/100 Pass 1 1 1 10.0 20 40 10 N.C. N.C. N.C. 0/100 Pass1 1 1 15.0 25 50 15 N.C. N.C. N.C. 0/100 Pass 1 1 1 20.0 30 60 20 0.120.05 0.04 0/100 Pass 1 1 1 30.0 40 60 5 0.20 0.05 0.05 0/100 Pass 1 1 18.0 0.5 3 10 1 N.C. N.C. N.C. 1/100 Pass 1 1 1 5.0 10 25 5 N.C. N.C.N.C. 1/100 Pass 1 1 1 10.0 20 40 10 N.C. N.C. N.C. 0/100 Pass 1 1 1 15.025 50 15 N.C. N.C. N.C. 0/100 Pass 1 1 1 20.0 30 60 20 0.13 0.05 0.040/100 Pass 1 1 1 30.0 40 60 5 0.21 0.04 0.05 0/100 Pass 1 1 1 N.C. = notcalculated

TABLE 7  

  Time in drying Pre-Condition 2 Observation on quality of 2^(nd) diplayer oven 1 Surface Water Latex Latex Rubber Thin/ (following TempContent Pick Flow Lump Weak 1^(st) dip) (° C.) (%) Up Mark FormationSpot Shrinkage  0 53 90.70 Good No No No Yes  2 51 74.64 Good No No NoNo  4 51 61.96 Good No No No No  6 48 67.04 Good No No No No  8 45 84.56Good No No No No  10 46 55.17 Good No No No No  12 48 69.17 Good No NoNo No  20 52 72.14 Good No No No No  40 44 73.35 Good No No No No  60 4273.76 Good No No No No  80 40 74.02 Good No No No No 100 42 68.75 GoodNo No No No 120 42 64.10 Good No No No No 150 44 63.07 Good No No No No180 41 64.38 Good No No No No 210 44 61.18 Good No No No No 240 45 48.10Good No No No No 300 39 29.22 Good No No No No  300* 44 29.34 Good No NoNo No 350 40 16.58 No No No No Yes  350* 43 16.79 No No No No Yes  350*41 21.66 No No No No No 400 44 26.87 No No No No Yes  400* 56 1.88 No NoNo No No 450 41 83.13 No No No No Yes  450* 41 6.00 No No No No No 50045 7.05 No Yes No No Yes 550 39 6.68 No Yes No No Yes 600 62 1.79 No YesNo No Yes 650 52 3.82 No Yes No No Yes 700 77 1.95 No Yes No No Yes 75075 0.81 No Yes No No Yes 800 70 0.93 No Yes No No Yes 850 73 0.62 No YesNo No Yes 900 73 4.00 No Yes No No Yes 950 80 2.76 No Yes No No Yes1000  91 3.07 No Yes No No Yes Pre-Condition 3 Time in Surface Temp (°C.) drying Sample Sample Observation on quality of 3^(rd) dip layer ovenwith first with second Water Latex Latex Rubber Thin/ following dippeddipped Content Pick Flow Lump Weak Shrink- 2^(nd) dip layer layer (%) UpMark Formation Spot age 0 58 50 77.81 Good No No No No 2 40 34 76.46Good No No No No 4 41 35 78.29 Good No No No No 6 49 39 76.00 Good No NoNo No 8 50 40 76.45 Good No No No No 10 49 41 77.21 Good No No No No 1249 39 76.47 Good No No No No 20 59 39 76.37 Good No No No No 40 42 3775.61 Good No No No No 60 41 38 69.58 Good No No No No 80 40 35 66.36Good No No No No 100 45 38 68.47 Good No No No No 120 42 39 71.07 GoodNo No No No 150 44 41 65.94 Good No No No No 180 46 42 55.10 Good No NoNo No 210 40 41 45.96 Good No No No No 240 44 37 51.54 Good No No No No300-1000 Not continued to third dip *Re-test

TABLE 8 Pre- Observations on the Drying Condition 2 quality of the2^(nd) latex layer Oven 1 Surface Water Latex Latex Rubber Thin/ TimeTemp Content Pick Flow Lump Weak Shrink- (sec) (° C.) (%) Up MarkFormation Spot age 240 40 55.43 Good No No No Yes 300 40 53.15 Good NoNo No No 350 40 47.20 Good No No No Yes 400 40 11.56 No Yes No No Yes450 40 21.51 No Yes No No Yes 500 40 4.06 No Yes No No Yes 550 40 2.08No Yes No No Yes 600 40 6.15 No Yes No No Yes 650 40 7.58 No Yes No NoYes 700 40 0.79 No Yes No No Yes 750 40 7.44 No Yes No No Yes 800 400.65 No Yes No No Yes 850 40 4.19 No Yes No No Yes 900 40 5.58 No Yes NoNo Yes 950 40 4.85 No Yes No No Yes 1000 40 5.38 No Yes No No Yes

TABLE 9A Propose Actual Pre- Surface Observations after 1^(st) dip layerCondition 1 Temp Observation Latex Latex Rubber Thin/ Surface After Ovenon first latex Pick Flow Lump Weak Shrink- Temp (° C.) Heating dip layerUp Mark Formation Spot age <25 25 Pick up okay Good Good No Yes No <3029 Pick up okay Good Good No Yes No 30-45 39 Pick up okay Good Good NoNo No 45-53 49 Pick up okay Good Good No No No 53-69 61 Pick up okayGood Good No No No 70 Pick up okay Good Moderate No No No 70-80 75 Pickup okay Good Moderate No No No 80 Pick up okay Good Moderate No No No80-85 84 Pick up okay Good Bad No No No 85-95 92 Pick up okay Good BadNo Yes Yes  95-120 106 Pick up okay Good Bad No Yes Yes >120 122 Pick upokay Good Bad No Yes Yes but gelling film shrinkage at palm

TABLE 9B Propose Pre-Condition 2 Observations after 2^(nd) dip layerPre- Surface Observation Condition 2 Temp Water on surface Latex Thin/Rubber Surface before 2^(nd) Content after 2^(nd) Dip Latex flow WeakLumps or Temp (° C.) Latex Dip (%) Layer Pick mark Spot Shrink-age <2525 64.24 Pick up okay Good Good No No 25-30 28 62.66 Pick up okay GoodGood No No 30-35 33 64.36 Pick up okay Good Good No No 35-55 45 23.14Pick up okay Good Good No No 55-65 60 1.13 Pick up okay Bad Bad Yes No65-75 70 2.23 Pick up okay Bad Bad Yes No 75-90 83 1.07 Pick up okay BadBad Yes No  90-120 105 0.92 Pick up okay Bad Bad Yes No >120 120 2.12Second layer of Bad Bad Yes No latex cannot be coated evenly on the1^(st) layer

TABLE 9C Propose Pre-Condition 3 Observations after 3^(rd) dip layerPre- Surface Observation Condition 3 Temp Water on surface Latex LatexThin/ Rubber Surface before 3^(rd) Content after 3^(rd) Dip Pick flowWeak Lumps or Temp (° C.) Latex Dip (%) Layer Up mark Spot Shrinkage <2523 61.62 Pick up okay Good Good No No 25-30 28 66.57 Pick up okay GoodGood No No 30-35 33 65.20 Pick up okay Good Good No No 35-55 46 39.54Pick up okay Good Good No No 55-65 70 0.46 Third latex layer Bad Bad NoNo 65-75 74 4.31 cannot be coated Bad Bad No No 75-90 83 2.88 on to thesecond Bad Bad No No  90-120 104 0.62 layer Bad Bad No No >120 121 0.64Bad Bad No No

TABLE 10 Pre- Drying Condition 2 Observations on 2^(nd) dipped layerOven Surface Water Latex Latex Rubber Thin/ Time Temp Content Pick FlowLump Weak (sec) (° C.) (%) Up Mark Formation Spot Shrinkage 10 49 74.84Good No No No No 20 54 66.76 Good No No No No 30 55 60.01 Good No No NoNo 40 56 67.36 Good No No No No 50 55 72.39 Good No No No No 60 55 62.65Good No No No No 70 55 69.36 Good No No No No 80 56 54.47 Good No No NoNo 110 58 52.43 Good No No No No 120 57 35.20 Good No No No No 130 6124.45 Good Yes No No No 140 50 20.51 No Yes No No No 170 53 5.56 No YesNo No No 200 54 2.30 No Yes No No No 230 80 9.27 No Yes No No No 260 855.08 No Yes No No No 290 88 7.69 No Yes No No No 320 116 2.03 No Yes NoNo No 350 137 3.56 No Yes No No No

Testing Techniques

For all of the Examples, the following testing techniques were used.

General Testing Procedures

The testing procedures were conducted in accordance with ASTM D 6319-00(Reapproved 2005), based on a 100 sample test size. This ASTM standardis available from ASTM International, and details the standardspecifications and testing standards used for testing nitrile rubberexamination gloves for medical applications. These tests can be appliedsimilarly to non-glove multilayer films.

Barrier Defects

The barrier defects test for detecting holes was conducted in accordancewith ASTM D 5151-06, which is incorporated within ASTM D 6319-00.

This test involves pouring a minimum of 1000 cm³ of water having a roomtemperature of 15° C. to 30° C. into the top of a mandral to which theglove is affixed. The glove is then visually assessed for immediatewater leakage and water leakage after 2 minutes. The extent of waterleakage by a sample of 100 gloves was rated as follows:

1=Excellent: <1/100

2=Good: 2/100

3=Average: 3/100

4=Poor: 4/100

5=Very Poor: 5/100

Water content

The water content of any film on a mould, which may be in the shape of aglove, is determined by the following method:

(i) Weigh the mould together with wet coated film (pre-condition film)and record the weight Y₁.

(ii) Dry (i) in an oven for 60 minutes at 120° C.

(iii) Place (ii) in a desiccator for 10 minutes for cooling.

(iv) Weigh (iii) and record the weight, Y₂ (dry film and mould).

(v) Calculate water content as ((Y₁−Y₂)/(Y₁−Y₀))×100%, where Y₀ is theuncoated mould net weight.

Stickiness of Gloves

Stickiness of gloves was assessed on a 100 glove sample size. The gloveswere assessed by persons who wear elastomeric gloves as part of theirwork and the level of stickiness of batches of 20 gloves at a time wasassessed, using the following rating system:

1=not sticky (“none”)

2=less sticky (“minimal”)

3=sticky (“sticky”)

4=very sticky (“very”)

5=very high stickiness (“high”)

The average of the 5×20 glove batches was assessed to the closest roundfigure to give the stickiness level for the 100 glove sample size.

Latex Pick-Up

Latex pick-up refers to the pick-up or wetting of the composition forforming an elastomeric film on the mould, or any outer coating or layeron the mould. This is determined by visual inspection as being good(marked “good”) or bad/absent (“poor”/“no”).

Latex Flow Mark

Latex flow mark refers to the appearance of a flow mark where thecomposition appears to flow off the mould, or off the composition thathas been coated or deposited prior to the subject coating. Causes of aflow mark can include a poor gel strength of the composition duringdipping whereby the composition takes a longer time to deposit on themould or previously deposited layer(s), poor pick-up or poor adhesion.This is assessed by visual inspection as being present (recorded as“yes”, or “bad” or “moderate” to indicate degree) or not present(recorded as “no” or “good”).

Evenness of Coating

Whether the coating is even is assessed visually, and recorded as being“even” or not even (“not”).

Adhesion between Layers of Elastomeric Film

Adhesion between layers is assessed by visual inspection during theprocess of dipping—that is, at the point at which the mould is withdrawnfrom the composition, or through assessment of the final product.

Rubber Lump Formation

Rubber lump formation refers to the formation of lumps of thecomposition for forming the elastomeric film on the mould, or arough/lumpy surface of the composition on the mould. This can beassessed at the point when the mould is withdrawn from the composition,or in the final product. This is assessed by visual inspection as beingpresent (recorded as “yes”) or not present (recorded as “no”).

Thin or Weak Spots

The presence or absence of thin or weak spots is tested by inflating thefinal product with air, and visually inspecting the product for thin orweak spots. Thin or weak spots are recorded as being present (“yes”) orabsent (“no”).

Shrinkage.

A small level of shrinkage is permitted in the products, and arises as aresult of the evaporation of moisture from the layers of composition forforming the elastomeric film. For a glove product of 27 cm in length (atthe point in time when the mould is withdrawn from the composition forforming the last layer), there is normally shrinkage of about 0.5 cm inlength after a few seconds (less than 10 seconds) from the point ofwithdrawal from the composition but before drying. In the case of aglove product, shrinkage of four times this level, or greater than 2 cmin a length of 27 cm, is considered to be an unacceptable level ofshrinkage, and is recorded in shrinkage testing tables as being present(“yes”). If the level of shrinkage is 1 cm or less, this is recorded asbeing not present (“no”).

Durability Testing.

The following test steps were taken to determine durability of gloves ina range of temperature and humidity conditions. The gloves were worn bypersons involved in a range of duties, including at least the followingthree duties: (i) office work, (ii) packaging of products into boxes and(iii) laboratory/quality control/R&D work.

1. Condition gloves for 30 minutes in desiccator.

2. Provide gloves to at least 3 testers involved in the threeduties—office work, packaging and laboratory work.

3. Record the time taken for the glove to tear when used by that tester.

4. Each tester tests 5 samples of gloves and records the time to tearingfor each sample.

For the 15 trial results, the average time before tearing of the glovesamples was determined. The durability was then classified as follows:

-   -   1 hours or less—poor durability (“poor” in table 6)    -   >1 hours to 3 hours—acceptable durability (“OK”)    -   >3 hours—good durability (“good”)

1. A method for producing multi-layered elastomeric film or article, themethod comprising: (i) dipping a mould into a composition for producingan elastomeric film having a total solids content of between 5%-40% toproduce a layer of elastomeric film composition on the mould, (ii)partially drying the layer of elastomeric film composition on the mouldto reduce the total water content of the elastomeric film composition toa level of not less than 22%, (iii) dipping the mould coated with thepartially dried layer of elastomeric film composition into a compositionfor producing an elastomeric film having a total solids content ofbetween 5%-40% to produce a further layer of elastomeric filmcomposition on the mould, (iv) optionally repeating the partial dryingstep (ii) and the further dipping step (iii), and (v) drying and curingthe layers of elastomeric film composition on the mould.
 2. The methodof claim 1, wherein the partial drying step (ii) is controlled to reducethe water content to a level below 90%, but not less than 22%.
 3. Themethod of claim 2, wherein the partial drying step (ii) is controlled toreduce the water content to a level below 80% but not less than 22%. 4.The method of claim 3, wherein the partial drying step (ii) iscontrolled to reduce the water content to a level below 80% but not lessthan 25%.
 5. The method of claim 4, wherein the partial drying step (ii)is controlled to reduce the water content to a level below 75% but notless than 25%.
 6. The method of claim 4, wherein the partial drying step(ii) is controlled to reduce the water content to a level below 77% butnot less than 30%.
 7. The method of claim 1, wherein the partial dryingstep (ii) is controlled so that at the end of partial drying the filmsurface temperature of the elastomeric film composition on the mould isbetween 25° C.-85° C.
 8. The method of claim 1, wherein the partialdrying step (ii) achieves a film surface temperature of between 30° C.and 80° C.
 9. The method of claim 1, wherein the partial drying step(ii) achieves a film surface temperature of between 40° C. and 80° C.10. The method of claim 1, wherein the partial drying step (ii)comprises subjecting the coated mould to drying conditions at atemperature above ambient.
 11. The method of claim 10 wherein thepartial drying step (ii) comprises applying drying radiation to thecoated mould.
 12. The method of claim 1, wherein the mould is subjectedto heating prior to dipping step (i).
 13. The method of claim 12,wherein the heating step comprises heating to raise the surfacetemperature to a temperature in the range of 25° C. to 85° C.
 14. Themethod of claim 1, further comprising the steps of: (a) dipping themould into a coagulant containing multivalent ions in solution, and (b)drying or partially drying the coagulant-dipped mould, prior to step(i).
 15. The method of claim 14, wherein the mould is heated prior todipping into the coagulant.
 16. The method of claim 15, wherein themould is heated to a surface temperature in the range of 30° C. to 70°C.
 17. The method of claim 14, wherein the multivalent ions aremultivalent metal ions.
 18. The method of claim 1, wherein the dwelltime of the mould in the dipping tank in step (i) is between 1.0 to 10.0seconds.
 19. The method of claim 1, wherein the temperature of thecomposition into which the mould is dipped in step (i) is within therange of 10° C. to 60° C.
 20. The method of claim 1, wherein the film orarticle has between 2 to 15 layers.
 21. The method of claim 1, whereinstep (iv) of repeating the partial drying step (ii) and the furtherdipping step (iii), is performed at least once.
 22. The method of claim21, wherein the film or article has between 3 and 15 layers.
 23. Themethod of claim 1, wherein each layer of the film constitutes between 6and 90% of the total film thickness.
 24. The method of claim 1, whereinthe composition for producing an elastomeric film comprises anelastomer-forming polymer and a cross-linking agent.
 25. The method ofclaim 1, wherein the mould is a glove-shaped mould, and the elastomericarticle is a glove.
 26. A film or article produced by the method ofclaim 1.